CN1740267A - Electroluminous organic small molecular phenothiazine material and its prepn process - Google Patents
Electroluminous organic small molecular phenothiazine material and its prepn process Download PDFInfo
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- CN1740267A CN1740267A CN 200510015129 CN200510015129A CN1740267A CN 1740267 A CN1740267 A CN 1740267A CN 200510015129 CN200510015129 CN 200510015129 CN 200510015129 A CN200510015129 A CN 200510015129A CN 1740267 A CN1740267 A CN 1740267A
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- phenothiazine
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Abstract
The present invention is electroluminous organic small molecular phenothiazine material and its preparation process. The present invention adopts phenothiazine as basic unit, and alters the conjugation of phenothiazine arene and the electron donor or electron acceptor radical of side chain to decrease or increase the band gap, so as to constitute the light emitting material. The preparation process of the electroluminous organic small molecular phenothiazine material includes three steps: 1. synthesis of N-alkyl phenothiazine dialdehyde monomer; 2. synthesis of aromatic phosphine salt monomer; and 3. the Witting condensation of these two kinds of monomer to obtain the electroluminous organic small molecular phenothiazine material. The organic electroluminous material can glow with green light, is soluble in common solvent and may be used in making light emitting devices through evaporation process or rotary painting process.
Description
[technical field]: patent of the present invention relates to a kind of novel electroluminous organic small molecular phenothiazine material and preparation method thereof.
[background technology]:
As the fresh combatants of technical field of flat panel display, organic electroluminescent (OLED) has related to different ambits such as materialogy, luminescence and microtronics, has outstanding high-performance aspect portable, dull and stereotyped and the flexible demonstration.Therefore, the research of OLED can not only drive the development of related discipline, and shows to have the huge market of potential in dull and stereotyped field.Electroluminescent organic material is mainly some conjugated organic molecule or polymer.The characteristics of organic molecule are that the variable range of its chemical structure is wide, introduce the conjugated degree that alkene, alkynes, aromatic ring etc. can change system in small molecules, thereby regulate the glow color of compound; In conjugated system, introduce different chromophores or the different groups that pushes away, draws electronic effect is arranged, can finely tune the electronic structure (energy band structure) of pi-conjugated system, and then the photoelectric properties of compound are changed.
Thiodiphenylamine is the heterogeneous ring compound of a class electron rich, contains two heteroatomss of nitrogen and sulphur in the thiodiphenylamine molecule, and the easy and phenyl ring formation delocalization structure of its lone-pair electron makes it have very strong fluorescent characteristic and structure regulating.Thiodiphenylamine and derivative thereof have lower ionizing potential, and easily lose an electronics and form corresponding radical cation, be stronger electronic donor group, can be used for electroluminescent and nonlinear optical material.The thiodiphenylamine molecule has stronger rigidity and non-copline configuration, because the distortion of thiodiphenylamine molecule can stop the formation of accumulation of π key and interchain exciplex, thereby might improve the efficient of EL material.
[summary of the invention]: the objective of the invention is in phenothiazines molecular conjugation system, to introduce different chromophores or the different groups that pushes away, draws electronic effect is arranged, so that the electronic structure (energy band structure) to pi-conjugated system is finely tuned, and then the luminescent properties of phenothiazines material institute structure device is changed, obtain a kind of phenothiazines electroluminous organic small molecular material and preparation method, and the luminescent properties of device, to increase the kind of electroluminescent organic material, satisfy the needs of novel light-emitting device.
Technical scheme of the present invention is:
With the thiodiphenylamine is elementary cell, by changing conjugacy and the confession of side chain or the band gap that drawing electron group reduces or increase material of thiodiphenylamine aromatic hydrocarbons, thereby make up the structure of luminescent material, the electroluminous organic small molecular phenothiazine material that this design forms has following structure:
In the said structure formula: R
1Be alkyl, alkyl chain length is 1-18; R
2, R
3, R
4, R
5Be hydrogen atom, phenyl, p-nitrophenyl, substituting group can be identical, also can be different.
The preparation method of electroluminous organic small molecular phenothiazine material provided by the invention comprises three steps: 1. N-alkyl phenothiazinyl dialdehyde is monomeric synthetic; 2. the aromatic phosphines salt monomer is synthetic; 3. two kinds of monomers are obtained required polymkeric substance by the Witting condensation reaction.Wherein:
(1) synthesizing of N-alkyl phenothiazinyl dialdehyde:
Under 0-55 ℃ temperature, N-alkyl thiodiphenylamine and phosphorus oxychloride are (1: 2-40) join in the dimethyl formamide, be warming up to 130 ℃ gradually, react stopped reaction after 2-10 hour under the induction stirring in molar ratio; After the reaction product cooling, through extraction, washing, dry, with silica gel column chromatography (sherwood oil: ethyl acetate=3: 1) refining, obtain the phenothiazinyl dialdehyde.
(2) synthesizing respectively of aromatic phosphines salt monomer is (1: 2-3) join in the dimethyl formamide in molar ratio with brooethyl benzene, diphenyl-chloromethane, 4-chloromethyl oil of mirbane and trimethyl phosphite; reacted 1-24 hour down in 120-140 ℃ under nitrogen protection, excessive trimethyl phosphite is removed in decompression.Resistates with silica gel column chromatography (eluent: ethyl acetate or sherwood oil: the mixed solvent of ethyl acetate=10: 1) refining, obtain three kinds of aromatic phosphines salt monomers.
(3) obtain electroluminous organic small molecular phenothiazine material by the Witting condensation reaction:
N-alkyl thiodiphenylamine dialdehyde monomer and aromatic phosphines salt monomer with preparation in above-mentioned (one) (two) step under nitrogen protection are dissolved in the anhydrous tetrahydro furan for (1: 2.2) in molar ratio; dripping mol ratio then is the methanol solution that 2-6 doubly measures the sodium methylate of (comparing with N-alkyl thiodiphenylamine dialdehyde monomer); under the room temperature stirring reaction 1-24 hour, stopped reaction then.The evaporate to dryness methanol solvate, washing, the employing chloroform extraction separates, with distilled water repetitive scrubbing organic phase, use anhydrous sodium sulfate drying at last, rotary evaporation concentrates, with silica gel column chromatography (sherwood oil: ethyl acetate=6: 1-10: 1 mixed solvent) make with extra care, obtain electroluminous organic small molecular phenothiazine material.
Advantage of the present invention and positively effect: the thiodiphenylamine molecule with conjugacy is a template, and the band gap that confession or the drawing electron group by side chain reduces or increase material is illustrated the influence of the structure of material to the device luminescent properties.
[embodiment]:
Embodiment 1
(1) N-n-octyl-3,7-dialdehyde-based thiodiphenylamine synthetic
Under 0-55 ℃ temperature, under nitrogen protection, N-alkyl thiodiphenylamine 9.3445g (30mmol) and phosphorus oxychloride 70ml (750mmol) are joined in the 60ml dimethyl formamide for (1: 25) in molar ratio, be warming up to 130 ℃ gradually, react stopped reaction after 6 hours under the induction stirring; After reaction product is cooled to 100 ℃, pour in the 350g ice, stir standing over night.Repeat repeatedly to extract with chloroform, dried over sodium sulfate is filtered.The lower black oily liquids is revolved steaming remove chloroform, with silica gel column chromatography (sherwood oil: ethyl acetate=3: 1) make with extra care, obtain N-n-octyl-3,7-dialdehyde-based thiodiphenylamine.Fusing point: 114.0-115.0 ℃
1H?NMR(CDCl
3，ppm)δ9.81(2H，s，CHO)，7.64-7.66(2H，d，2，8-Ar-H)，7.57(2H，s，4，6-Ar-H)，6.93-6.95(2H，d，1，9-Ar-H)，3.90-3.93(2H，t，ArN-CH
2)，1.78-1.85(2H，m，β-CH
2)，1.24-1.45(10H，m，CH
2)，0.84-0.87(3H，t，CH
3)。
Can confirm to have following structure thus:
(2) the phenmethyl dimethyl phosphate is synthetic
The trimethyl phosphite of 5.1311g (0.03mol) brooethyl benzene and 8.5636g (0.069mol) is joined in the dimethyl formamide, reacted 8 hours down in 140 ℃ under nitrogen protection, excessive trimethyl phosphite is removed in decompression.Resistates silica gel column chromatography (sherwood oil: ethyl acetate=1: 2) refining.Obtain the phenmethyl dimethyl phosphate.Golden yellow liquid, yield 71.4%.
(3) the Witting condensation reaction synthesizes 3,7-pair-(phenyl-vinyl)-10-octyl group-thiodiphenylamine (being abbreviated as PTH-I)
Under nitrogen protection, 1.1026g (3mmol) N-octyl group thiodiphenylamine dialdehyde and 1.2611g (6.3mmol) phenmethyl dimethyl phosphate are dissolved in the 50ml anhydrous tetrahydro furan; drip the methanol solution that contains 0.5g (9.0mmol) sodium methylate then; stirring reaction is 12 hours under the room temperature, then stopped reaction.The evaporate to dryness methanol solvate, washing adopts chloroform extraction to separate, with distilled water repetitive scrubbing organic phase, use anhydrous sodium sulfate drying at last, rotary evaporation concentrates, with silica gel column chromatography (sherwood oil: ethyl acetate=10: 1) make with extra care, get the yellow-green colour solid, productive rate 47.8%.Fusing point 123-124 ℃.
Nmr analysis:
1H NMR (CDCl
3): δ 0.96 (3H, t, CH
3), 1.33 (2H, m, CH
2CH
3), 1.29 (8H, m, NCH
2CH
2(CH
2)
4), 1.52 (2H, m, NCH
2CH
2), 3.06 (2H, t, NCH
2), 6.99 (4H, s, Ar-CH=CH), 7.07-7.42 (16H, m, ArH) ppm
Infrared analysis: IR (KBr, cm
-1): 3023 (m, Ar-H), 2955 (s ,-CH
3), 2922 (s, aliphaticCH), 2852 (m,＞N-CH
2-), 1195 (m, C-N), 1295,963 (s ,-CH=CH-)
Can confirm to have following structure thus:
Performance: solid fluorescence is emitted as 528nm, and structure is mixed for the ITO/ Polyvinyl carbazole: PTH-I (2: 1)/Ca/Al individual layer electroluminescent device green light, and emission peak λ max=520nm, opening bright voltage is 7V; High-high brightness is 3.6cd/m
2(15V)
Embodiment 2
(1) N-n-octyl-3,7-dialdehyde-based thiodiphenylamine synthetic
With embodiment 1
(2) the diphenyl-methyl dimethyl phosphate is synthetic
The trimethyl phosphite of 2.0268g (10mmol) diphenyl-chloromethane and 2.4487g (19.73mmol) is joined in the dimethyl formamide, reacted 14 hours down in 140 ℃ under nitrogen protection, excessive trimethyl phosphite is removed in decompression.Resistates is refining with silica gel column chromatography (ethyl acetate).Get Off-white solid diphenyl-methyl dimethyl phosphate, productive rate 65%.Fusing point 98-99 ℃.
(3) the synthetic N-octyl group-3 of Witting condensation reaction, 7-pair-(2,2-phenylbenzene-vinyl)-thiodiphenylamine (being abbreviated as PTH-II)
Under nitrogen protection, 0.62g (1.6326mmol) N-octyl group thiodiphenylamine dialdehyde and 1g (3.6196mmol) diphenyl-methyl dimethyl phosphate are dissolved in the 45ml anhydrous tetrahydro furan; drip the methanol solution that contains 0.44g (8.163mmol) sodium methylate then; stirring reaction is 12 hours under the room temperature, then stopped reaction.The evaporate to dryness methanol solvate, washing, the separation of employing chloroform extraction with distilled water repetitive scrubbing organic phase, is used anhydrous sodium sulfate drying at last, and rotary evaporation concentrates, with silica gel column chromatography (sherwood oil: ethyl acetate=10: 1) make with extra care, get yellow solid.Productive rate: 36.48%.Fusing point: 82-84 ℃.
Nmr analysis:
1H NMR (CDCl
3): δ 0.96 (3H, t, CH
3), 1.33 (2H, m, CH
2CH
3), 1.29 (8H, m, NCH
2CH
2(CH
2)
4), 1.52 (2H, m, NCH
2CH
2), 3.06 (2H, t, NCH
2), 6.92 (2H, s, Ar-C (Ar)=CH), 7.07-7.42 (26H, m, ArH) ppm infrared analysis: IR (KBr, cm
-1): 3055 (m ,-C=CH-), 3023 (m, Ar-H), 2952 (s ,-CH
3), 2924 (s, aliphatic CH), 2853 (m,＞N-CH
2-), 1212 (m, C-N), 807 (s ,-C=CH-)
Can confirm to have following structure thus:
Performance: device architecture mixes for the ITO/ Polyvinyl carbazole: PTH-II (2: 1)/Ca/Al individual layer electroluminescent device green light, and emission peak λ max=528nm, opening bright voltage is 6V; Maximum luminousing brightness is 8.2cd/m
2(15V); Device architecture is the emission peak λ max=557nm of the double-deck electroluminescent device of ITO/PTH-II/PBD/Mg:Ag/Ag, and luminosity is 10.7cd/m
2(9V).
Embodiment 3
(1) N-n-octyl-3,7-dialdehyde-based thiodiphenylamine synthetic
With embodiment 1
(2) 4-oil of mirbane methyl dimethyl phosphate is synthetic
The 4-chloromethyl oil of mirbane of 5.147g (0.03mol) and the trimethyl phosphite of 11.1668g (0.09mol) are joined in the dimethyl formamide, reacted 12 hours down in 140 ℃ under nitrogen protection, excessive trimethyl phosphite is removed in decompression.Resistates silica gel column chromatography (eluent: ethyl acetate) refining.Obtain 4-oil of mirbane methyl dimethyl phosphate.Reddish-brown liquid, productive rate 41%.
(3) the Witting condensation reaction synthesizes 3,7-pair-((4-nitro)-phenyl-vinyl)-10-octyl group-thiodiphenylamine (being abbreviated as PTH-III)
Under nitrogen protection, 0.3675g (1.0mmol) N-octyl group thiodiphenylamine dialdehyde and 0.5394g (2.2mmol) 4-oil of mirbane methyl dimethyl phosphate are dissolved in the 30ml anhydrous tetrahydro furan; drip the methanol solution that contains 0.22g (4.0mmol) sodium methylate then; stirring reaction is 12 hours under the room temperature, then stopped reaction.The evaporate to dryness methanol solvate, washing, the separation of employing chloroform extraction with distilled water repetitive scrubbing organic phase, is used anhydrous sodium sulfate drying at last, and rotary evaporation concentrates, with silica gel column chromatography (sherwood oil: ethyl acetate=6: 1) make with extra care, get the reddish-brown solid.Productive rate 36.82%.Fusing point: 61-62 ℃
Nmr analysis:
1H NMR (CDCl
3): δ 0.96 (3H, t, CH
3), 1.33 (2H, m, CH
2CH
3), 1.29 (8H, m, NCH
2CH
2(CH
2)
4), 1.52 (2H, m, NCH
2CH
2), 3.06 (2H, t, NCH
2), 7.13 (1H, m, NO
2Ar-CH), 7.28 (1H, m, ArCH=CH), 7.68-8.19 (14H, m, ArH) ppm infrared analysis: IR (KBr, cm
-1): 3400 (m, Ar-H), 2955 (s ,-CH
3), 2922 (s, aliphaticCH), 2852 (m,＞N-CH
2-), 1555～1487,1357～1318 (s, C-NO
2), 1195 (m, C-N), 675 (s ,-CH=CH-)
Can confirm to have following structure thus:
Performance: device architecture is the mix maximum luminous peak position 532nm of double-deck electroluminescent device of ITO/ Polyvinyl carbazole doping PTH-III (2: 1)/PBD/Mg:Ag/Ag.The device green light; The bright voltage that opens of device is 10V; Maximum luminousing brightness is 2.2cd/m
2(20V).
Claims (5)
1. electroluminous organic small molecular phenothiazine material is characterized in that having following structure:
In the said structure formula: R
1Be alkyl, alkyl chain length is 1-18; R
2, R
3, R
4, R
5Be hydrogen atom, phenyl, p-nitrophenyl, substituting group can be identical, also can be different.
2. the preparation method of the described electroluminous organic small molecular phenothiazine material of claim 1 is characterized in that this method comprises three steps: 1. N-alkyl thiodiphenylamine dialdehyde is monomeric synthetic; 2. the aromatic phosphines salt monomer is synthetic; 3. two kinds of monomers are obtained required electroluminous organic small molecular phenothiazine material by the Witting condensation reaction.
3. the preparation method of luminescent material according to claim 2, it is characterized in that monomeric the synthesizing of N-alkyl thiodiphenylamine dialdehyde: under 0-55 ℃ temperature, under nitrogen protection, N-alkyl thiodiphenylamine and phosphorus oxychloride are (1: 2-40) join in the dimethyl formamide in molar ratio, be warming up to 130 ℃ gradually, react stopped reaction after 2-10 hour under the induction stirring; After reaction product is cooled to 100 ℃, pour in the ice, stir standing over night, repeat repeatedly to extract with chloroform, dried over sodium sulfate is filtered, the lower black oily liquids is revolved steaming remove chloroform, with silica gel column chromatography (sherwood oil: ethyl acetate=3: 1) make with extra care, obtain the phenothiazinyl dialdehyde.
4. the preparation method of luminescent material according to claim 2; it is characterized in that synthesizing of aromatic phosphines salt monomer: respectively brooethyl benzene, diphenyl-chloromethane, 4-chloromethyl oil of mirbane and trimethyl phosphite are (1: 2-3) join in the dimethyl formamide in molar ratio; under nitrogen protection, reacted 1-24 hour down in 120-140 ℃; excessive trimethyl phosphite is removed in decompression; resistates with silica gel column chromatography (eluent: ethyl acetate or sherwood oil: the mixed solvent of ethyl acetate=10: 1) refining, obtain three kinds of aromatic phosphines salt monomers.
5. the preparation method of luminescent material according to claim 2; it is characterized in that the Witting condensation reaction is: under nitrogen protection with claim 3 in the N-alkyl thiodiphenylamine dialdehyde monomer of preparation and the claim 4 the aromatic phosphines salt monomer of preparation be dissolved in the anhydrous tetrahydro furan for (1: 2.2) in molar ratio; dripping mol ratio then is the methanol solution that 2-6 doubly measures the sodium methylate of (comparing with N-alkyl thiodiphenylamine dialdehyde monomer); under the room temperature stirring reaction 1-24 hour; stopped reaction then; the evaporate to dryness methanol solvate; washing; the employing chloroform extraction separates; with distilled water repetitive scrubbing organic phase; use anhydrous sodium sulfate drying at last; rotary evaporation concentrates; with silica gel column chromatography (eluent: sherwood oil: ethyl acetate=6: 1-10: 1 mixed solvent) make with extra care, obtain electroluminous organic small molecular phenothiazine material.
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|---|---|---|---|---|
| CN104177358A (en) * | 2013-05-28 | 2014-12-03 | 海洋王照明科技股份有限公司 | Bipolar blue light phosphorescent material, preparation method and organic electroluminescent device thereof |
-
2005
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177358A (en) * | 2013-05-28 | 2014-12-03 | 海洋王照明科技股份有限公司 | Bipolar blue light phosphorescent material, preparation method and organic electroluminescent device thereof |
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